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By AIME AIME

0 N March 5, at Carnegie Hall, Cleveland, the Ohio Section held a joint meeting with the Cleveland Engineering Society, and the local sections of the American Chemical Society, American Society of Mechanical Engineers, and the American Society for Steel Treating. Prior to the meeting there was an informal dinner attended by 50 men. Then followed an address, "The Principles of Corrosion Protection," by Ulick R. Evans, the well-known British specialist in this problem. There were 266 present, presided over by Zay Jeffries, president of the American Society for Steel Treating and a member of the Cleveland Engineering Society. The address was well received and some discussion followed

Jan 1, 1929

By L. Russell Van Wert

DURING an investigation in which the solubility relations of the phases in Muntz metal (60 per cent. copper, 40 per cent. zinc) were under study, certain phenomena that had no immediate connection with the main problem were observed, which were thought sufficiently interesting to study further. Because of lack of time, only a preliminary survey was made of two of these; namely, the cleavage structure developed under certain conditions in a 60:40 brass and abnormal grain growth in this alloy. CLEAVAGE STRUCTURE IN HEAT-TREATED MUNTZ METAL Carpenter noted many years ago that cold-working a brass of the Muntz metal type, which had been quenched previously from within the beta field, results in a partial breakdown of the supersaturated beta solution and the precipitation of the solute (the alpha solution) in the cleavage planes of the beta grains. This manner of rejection of a solute from a metastable solid solution is not peculiar to this particular alloy, for among others, it occurs in the cold-working of certain austenitic steels; for example, the austenitic nickel steels. In these ferrous alloys, cold deformation produces a partial decomposition of the austenite, with the formation of martensitic "needles" and zigzags in the austenitic poly-hedra. It is interesting to note that while the two solid solutions-austenite and quenched Muntz metal- are metastable and in their mode of decomposition behave quite alike when deformed in the cold, the metastability of each results from a different cause; viz., that of the austenite from the fact that it is a supercooled solution (its solvent, gamma iron, at ordinary temperatures is below its normal stable range) whereas the metastability of the quenched Muntz metal is the result of supersaturation.

Jan 1, 1929

By A. F. Crawley

THIS communication reports measurements of the densities of dilute liquid alloys of 0.1 and 0.5 pct Ag in Sn over temperature ranges of 170" and 210°C, respectively, above the melting point of pure tin (232°C). The work was earried out to provide accurate density data for some liquid diffusion studies performed by Davis.1 Densities were measured using a pycnometric technique established in this laboratory. Earlier papers2, 4 attest to the accuracy of ±0.05 pct and the reliability of the method. Tin, 99.999 pct pure, and silver 99.99 pct pure, were melted in a graphite crucible in a vacuum furnace and held at temperature for 10 hr to ensure homogenization. Ingots suitable for machining

Jan 1, 1970

By P. de Vitry, Willis P. Mould

The wire saw is a tool not less than 60 years old, probably nearer 100 years old. It was developed in Europe and is reputed to have originated in Belgium. Frombold is said to be the original patentee. Wire sawing equipment, as indicated in Fig. I, is very simple. It consists of a three-strand wire cable, usually pis or 1/4 in. in diameter, or a single flat ribbon of medium hard, tough, alloy steel twisted into a helix of those diameters, made to form an endless belt of any length up to several thousand feet. The wire is guided into the cut by sheaves mounted in slides on steel columns situated close to either end of the cut. The feed motion usually is controlled either by gravity or by hand-operated feed screws. The steel columns or "standards" range from 15 to 30 ft. in length. At the top is a swiveled arm supporting a sheave similar to the traveling sheave below. Immediately under the swivel-mounted sheave is a guy plate or collar with shackles attaching four chain or wire-rope guys with suitable tightening devices, or with two guys and two jack legs for supporting the standard vertically or at any desired anale. The usual drive is by a 10-hp. motor through a gear reducer, on which are Insti- two grooved sheaves, One of which is keyed and the other free running On the shaft. Tension is provided by a car running on a track in line with the driving sheave

Jan 1, 1948

By P. de Vitry, Willis P. Mould

The wire saw is a tool not less than 60 years old, probably nearer 100 years old. It was developed in Europe and is reputed to have originated in Belgium. Frombold is said to be the original patentee. Wire sawing equipment, as indicated in Fig. I, is very simple. It consists of a three-strand wire cable, usually pis or 1/4 in. in diameter, or a single flat ribbon of medium hard, tough, alloy steel twisted into a helix of those diameters, made to form an endless belt of any length up to several thousand feet. The wire is guided into the cut by sheaves mounted in slides on steel columns situated close to either end of the cut. The feed motion usually is controlled either by gravity or by hand-operated feed screws. The steel columns or "standards" range from 15 to 30 ft. in length. At the top is a swiveled arm supporting a sheave similar to the traveling sheave below. Immediately under the swivel-mounted sheave is a guy plate or collar with shackles attaching four chain or wire-rope guys with suitable tightening devices, or with two guys and two jack legs for supporting the standard vertically or at any desired anale. The usual drive is by a 10-hp. motor through a gear reducer, on which are Insti- two grooved sheaves, One of which is keyed and the other free running On the shaft. Tension is provided by a car running on a track in line with the driving sheave

Jan 1, 1948

By E. M. Furness, A. S. Henderson

ORIGINALLY the Babbitt experimental plant grinding circuit consisted of one rod mill 10 ½ ft diam by 12 ft long in open circuit followed by two ball mills 10 ½ ft diam* 12 ft long in parallel circuit. Shortly after operations commenced it was apparent that the rod mill could not function satisfactorily at the required 125 gross tons of ore per hr. Attempts to operate at this rate produced: 1) excessive tramp material over rod mill trommel screen which could not be handled in this open circuit and 2) excess build-up of coarse ore in the ball mill circuits because of inadequate rod mill grinding. Since Reserve Mining Co. ore must be ground to 85 pct -325 mesh to produce a satisfactory iron concentrate, an efficient and controlled grinding circuit is highly important. The first step in trying to resolve this grinding problem was to determine which unit of the circuit was actually in trouble and to what extent. A series of tests conducted at a lower tonnage rate of rod mill feed indicated that one ball mill could grind satisfactorily at rates up to 70 gross tons of rod mill feed per hr.

Jan 12, 1957

By Michael Richings

Although the role of slope stability has not changed, there have been changes in the mining industry which affect the geotechnician engaged in slope stability studies. The deposits currently being mined or evaluated are technically difficult , capital intensive, and economically marginal. In addition, many mining companies are now either controlled by oil companies or are financing projects through bank loans. The mining investor or decision maker is, therefore, often more sophisticated financially, but less sophisticated in mining terms. The impact of these changes will be to force the geo- technician and mining engineer to attempt to quantify risk and financial implications of a slope design. In conclusion, this paper outlines several questions which mining engineers should be asking those engaged in geotechnical studies and indicates the necessity for the mining engineer and geotechnician to work together and quantify the financial risk associated with a geotechnical design.

Jan 1, 1983

By Earle Schumacher

THE solidus line above the solid solution field in the lead-antimony system was originally determined by Dean and his associates1 from heating curves. They did not regard this line as having been accurately fixed and in their more recent publications2 the curves drawn do not follow closely the original data. The precise location of the solidus line is of importance in the extrusion of lead-antimony cable sheath, as the temperature of the metal in this process must be less than the lowest temperature at which any part of the alloy in the lead-press charge becomes liquid. It is very desirable, however, to operate at as high a temperature as possible, as the rate of extrusion for a given pressure is approximately doubled for an increase of 10° C. in temperature. The precise location of this line is also important, in the investigation of ternary systems of lead, antimony and a third metal. For these reasons, and because of the differences reported in the literature, data were secured on the lead-antimony solidus line by the classical quenching-test procedure.

Jan 1, 1927

(Under this heading will be published notes sent to the Secretary of the Institute by members or other persons. ) A member, technically educated, with 20 years' practical experience as engineer, assistant superintendent, superintendent, and manager of large mines and mills on construction and operation, also experience in mine examination, is open to engagement. Metallurgist of 18 years' experience in Mexico with large plants is open to engagement. Last position, superintendent of copper smelting works. Best line, copper and lead smelting, but also experienced in mine valuation and ore-treatment investigation work. Speaks Spanish. A member of the Institute and graduate mining engineer with 10 years' experience in the Lake Superior copper district, also practical experience, desires position as superintendent or manager. Member, graduate mining engineer, experienced in mine and mill work, geology and field work, one year in the hydrometallurgy of copper, is open for engagement Aug. 15. A member, at present in the Southwest., desires a position as assistant superintendent or assistant manager with a mining company operating in Washington or Alaska. Experienced assayer and engineer. A member, technical graduate, with nine years' mining experience as assayer, engineer, foreman, manager's assistant, and superintendent of large development and operating mining companies in the United States and Mexico, is open for engagement. A member, technical graduate, 33 years of age, 11 years' experience as chemist, metallurgist and superintendent of lixiviation plant and in charge of construction of cyanide mill, desires position as assistant superintendent or superintendent of mining or milling company in United States or Canada. Young man, technical graduate, two and a half years' experience in chemical laboratory, desires position as chemist.

Jan 9, 1913

By O&apos, R. G. Meara, M. M. Fine

One of the principal activities of the Bureau of Mines connected with the recent war was to help to increase the supply of strategic and critical minerals. Fluorite was one of the most critical of the nonmetallic minerals because of the increased demand for it as a flux in basic open-hearth and electric steel furnaces and as a raw material for the production of artificial cryolite used in the aluminum industry. Wartime developments in the technology of hydrofluoric acid, such as the use of the anhydrous acid as a catalyst in production of high-octane gasoline and the use of organic fluorides as carriers for insecticides, also increased the demand for acid-grade fluorite. † In 1943 the consumption of acid-grade fluorite was advancing at a more rapid rate than production, and was only slightly less than production during the latter half of the year.' The outlook for the postwar market for fluorite is encouraging Steel production is expected to remain high until the domestic demand for commodities not manufactured during the war is satisfied. The uses for hydrofluoric acid are expected to increase under the impetus of war-initiated research. In consideration of these and other factors some authorities predict a postwar demand for fluorite equal to about 60 to 75 per cent of the wartime production.1,2 Others believe that the postwar fluorite industry will be permanently expanded over its prewar status3 Acknowledgment This paper is one of many reporting on various aspects of the Bureau of Mines program directed toward the more effective utilization of our mineral resources. The program has been under the general supervision of R. S. Dean, Assistant Director, since July 1942. The scope of the paper falls in the province of the Metallurgical Branch, whose activities embrace the separation of difficultly beneficiated ores, the production of pure metals from domestic deposits, the exploitation of marginal ore reserves, the recovery of secondary metals, and the improvement of present industrial metallurgical practice. The investigation was initiated at the request of Mr. J. H. Steinmesch, vice-president and general manager, Minerva Oil Co., Eldorado, Ill. His hearty cooperation and helpful suggestions, and those of Mr. 0. E. Anderson, mill superintendent,

Jan 1, 1947

By M. M. Fine, R. G. Meara, O&apos

One of the principal activities of the Bureau of Mines connected with the recent war was to help to increase the supply of strategic and critical minerals. Fluorite was one of the most critical of the nonmetallic minerals because of the increased demand for it as a flux in basic open-hearth and electric steel furnaces and as a raw material for the production of artificial cryolite used in the aluminum industry. Wartime developments in the technology of hydrofluoric acid, such as the use of the anhydrous acid as a catalyst in production of high-octane gasoline and the use of organic fluorides as carriers for insecticides, also increased the demand for acid-grade fluorite. † In 1943 the consumption of acid-grade fluorite was advancing at a more rapid rate than production, and was only slightly less than production during the latter half of the year.' The outlook for the postwar market for fluorite is encouraging Steel production is expected to remain high until the domestic demand for commodities not manufactured during the war is satisfied. The uses for hydrofluoric acid are expected to increase under the impetus of war-initiated research. In consideration of these and other factors some authorities predict a postwar demand for fluorite equal to about 60 to 75 per cent of the wartime production.1,2 Others believe that the postwar fluorite industry will be permanently expanded over its prewar status3 Acknowledgment This paper is one of many reporting on various aspects of the Bureau of Mines program directed toward the more effective utilization of our mineral resources. The program has been under the general supervision of R. S. Dean, Assistant Director, since July 1942. The scope of the paper falls in the province of the Metallurgical Branch, whose activities embrace the separation of difficultly beneficiated ores, the production of pure metals from domestic deposits, the exploitation of marginal ore reserves, the recovery of secondary metals, and the improvement of present industrial metallurgical practice. The investigation was initiated at the request of Mr. J. H. Steinmesch, vice-president and general manager, Minerva Oil Co., Eldorado, Ill. His hearty cooperation and helpful suggestions, and those of Mr. 0. E. Anderson, mill superintendent,

Jan 1, 1947

By J. E. Johnson

The subject of blast-furnace slag is one which has had much consideration, particularly from the scientific standpoint, and several years ago technical literature contained many learned discussions on the oxygen-ratio of the acids and the bases, all on the assumption that acids and bases must be present in a ratio depending on molecular weight and chemical valency. Much work has also been don.e, sometimes in conjunction with the former, on the total heat and the temperature of initial fusion or softening of various slags. A wider knowledge of the blast-furnace now enables us to say that for practical purposes this work has been of almost no value. It is now generally admitted that on,the physical side the important point of a given slag is neither its total heat of fusion nor its softening-point, but its free-running temperature, since this is the critical temperature of the furnace. This temperature bears no definite relation to the softening-temperature, as determined by Seger cones, for instance, because some slags melt relatively like ice, with a very short viscous-range, while others melt relatively like tar, with a very long viscous-range. In one the difference between the softening- and the free-running temperature may be very small, as little as 100° F., while in another this difference may easily be 200' or 300°. The importance of this difference is so great in practice as to destroy completely the value of exhaustive investigations, even such as those of 0. Boudouard, published a few years ago.'

Jan 1, 1913

By Frank H. Kingdon

and eventually we would have trouble. That is, these little localized overstresses may not be important if the structure is loaded a few times, but may be important if the structure is loaded many thousands of times. The existence of localized stress has been demonstrated by direct experimentation with delicate extensometers by the elaborate investigations of Coker. Localized stresses four, five, and six times those that we would get by the ordinary laws of mechanics exist in most of our structures. These stresses, ordinarily, under steady load do no damage but if they are repeated many times may start progressive failure. So far, we have seen no failure that could not be explained by localized high stress at a nick, a crack, a point where one heat treatment stopped and another began, or where there was local faulting, or any one of a dozen causes. In the case of drill rods, the actual distribution of stress must be different from that which any mathematical analysis could predict. It would seem that the spread of damage from the localized overstresses, so far as we can see now, explains the phenomenon known as fatigue. The Ideal Drill Steel By Frank H. Kingdon The essential qualities of a drill steel are: (I), It must be easily forged; (2), the forged bit end must permit easy heat treatment to obtain hardness to resist chipping; (3)) the bar or body must be stiff to resist bending or twisting and yet tough to resist shock and vibration, with resulting breakage, (4), the forged shank end must be easily heat treated to obtain hardness with great toughness. Minor requirements are that the bit and the shank are in alignment with the body; that the shank is of the proper shape and length and the shank collar or lugs of the proper diameter and length; that the hole is free from obstruction; that the striking end of the shank is flat and square; that the bit is of the proper shape, with the cutting and reaming edges formed full and to the required size; that the reaming edges are concentric with the axis of the steel, and that there are no sharp corners at the shoulder where the bit blends into the body. The essential qualities of a bit, are: That its shape be such that maximum cutting speed can be maintained for as great a distance as possible before wear of the gage and cutting edge reduces the speed of penetration to a point where a change of steel is made necessary; that the size or diameter of the drill hole corresponding to the gage of the bit can be maintained with the least possible reduction as the depth of the hole increases, and that the bit can be correctly and readily formed and heat treated. The following features of bit design require attention: Shape,

Jan 1, 1922

By R. R. Sayers

Ventilation may be defined as the process by which vitiated air of an enclosed or partly enclosed space is continuously replaced by fresh air. Fresh air has been defined as invigorating pure air. Pure dry air at sea level contains the following gases:1 Analysis of Air at Sea Level Per Cent. Oxygen.................................................. 20.94 Nitrogen................................................. 78.09 Carbon dioxide........................................... 0.03 Argon................................................... 0.94 Helium, krypton, neon, xenon, hydrogen, hydrogen peroxide, ammonia, ozone........................................ traces Carbon Dioxide Limit For many years carbon dioxide was used as an index of the purity of the air vitiated by the metabolism of people. It was, however, well known that the untoward effects produced on those exposed to such air was not due to the concentration of the carbon dioxide. It has been found that the untoward effects on the comfort and efficiency of those so exposed are due to the increased temperature and humidity. It has been found that men can breathe air containing many times the amount of carbon dioxide found in our worst ventilated theaters and assembly halls, which, according to Rosenau, do not contain above 0.5 per cent, carbon dioxide. Nevertheless, in mines it sometimes occurs in sufficient quantities to cause symptoms in men or even unconsciousness and death. One-half of 1 per cent. of carbon dioxide in normal air causes a slight and unnotice-able increase in the ventilation of the lungs, that is, a man exposed to one-ha,lf of 1 per cent. of carbon dioxide will breathe a little deeper and a little faster than when in pure air. If 2 per cent. of carbon dioxide is in the air, the lung ventilation will be increased about 50 per cent.; if there

Jan 1, 1927

By W. M. Fox, D. P. Detwiler

IN the course of research on semiconducting inter-metallic compounds, it became necessary to obtain gallium metal of greater purity that that available commercially. Several methods were considered for further purification, including acid leaching,' fractional crystallization,' and zone-refining.3-5 The method of fractional crystallization was discarded as being equivalent to zone-refining in purification but inefficient in material and time. Both acid leaching and zone-refining were tried, and the method finally adopted is a combination of the two. The acid leaching technique has been reported' to produce gallium in which no impurities are detectable spectroscopically. Although this method is very effective in removing oxides and surface contaminants, semiconducting material made of gallium subjected only to leaching indicated little reduction in the concentration of metallic impurities. Zone-refining, however, appears very effective in removing trace metallic impurities, but comparatively ineffective in removing the surface oxide film. Consequently, the method evolved consists of acid leaching to thoroughly clean the surface, followed by zone-refining to remove metallic impurities. The low melting point and relatively high thermal conductivity of gallium introduce some difficulty in maintaining frozen and molten zones in zone-refining. To accomplish this, it is found necessary to reduce the effective ambient temperature by circulating ice water in coils about the regions that are to be kept frozen, while heat is supplied to the molten regions by resistance coils. The power supplied to the heating coils is regulated by a constant-voltage transformer and a variable autotransformer. Both heating and cooling coils are mounted on a transite base. The gallium ingot is held in a closed pyrex tube sliding inside the heating and cooling coils, the reciprocating method of Tanenbaum et al. being employed to move the molten zones through the ingot at a rate of 2 in. per hr. This apparatus is shown in Fig. 1. The results of a spectroscopic analysis f a zone-refined ingot, as well as of the material as-received and after acid leaching, are shown in Table I. The ingot was 32 cm in length, and received 37 molten-zone passes, the molten zone being about 4 cm long. The only impurity found was lead, the following elements being reported also as checked but not found in the pure material: Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cb, Cu, Ge, Au, Fe, Mg, Mn, Mo, Ni, Pt, Si, Ag, Na, Sr, Sn, Te, Ti, W, V, Zn, and Zr. There thus appears no indication of pickup of Al, Mg, or Si from the pyrex boat as reported by Zimmerman' in his fractional crystallization. Thus it appears that definite removal of lead from gallium occurs during the zone-refining process. It also may be concluded that a more sensitive analytical procedure than spectroscopy is required to evaluate quantitatively the purity of zone-refined metals. One such procedure which is proposed for use in the near future is the measurement of very low temperature resistivity. Although this will not identify the impurities present, it offers a very sensitive check of total impurity. Acknowledgment This work was supported by the Air Research and Development Command, United States Air Force.

Jan 1, 1956

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

The effects of increasing hydrogen content, introducing a notch, and changing the strain rate on properties of titanium and one of its alloys were investigated over a range of testing temperatures from —196° to 200°C. Both high purity and commercial purity A-55 titanium were used as representative a materials, while a commercial Ti-8 pct Mn alloy was used for an a-P alloy. It was found possible to analyze the data, using the ductile-to-brittle transition temperature concept. Increasing hydrogen, the presence of a notch, and increasing the testing speed raised the transition temperature for the a materials. The presence of hydrogen and notches raised the transition temperature of the a-B alloy also. However, increasing the testing speed generally decreased the transition temperature of the a-p alloy. IN previous papers, the authors have shown that hydrogen is most detrimental to the notch-bend impact toughness of a-titanium' and to the tensile ductility of a-B titanium alloys.' These general effects have been confirmed by Kessler and co-workers," and by Kotfila and Erbin." Kessler showed that the slower strain rate in notch-rupture tests was a more sensitive measure of hydrogen embrittle-ment of a-B alloys than the tensile test. In the present paper the authors cover, with tensile and notch-bend tests, the effect of testing speed, notches, and testing temperature on hydrogen em-brittlement. High purity and commercial purity titanium, examples of u materials, and a commercial a-,f3 Ti-8 pct Mn alloy were investigated. The purpose of the investigation was to correlate the factors producing embrittlement. Materials The high purity titanium for this investigation was obtained by arc-melting crystal bar from Foote Mineral Co. into 1 Ib ingots. As-cast hardnesses for these ingots ranged from 60 to 90 Brinell. The arc-melted ingots were forged to % in. diam rods at 1470°F. These rods were swaged to & in. diam at room temperature prior to machining of the specimens for hydrogenation and testing. The commercial A-55 titanium and the Ti-8 pct Mn alloy were obtained from Rem-Cru Titanium Inc., as % in. diam rod. The A-55 titanium was hot swaged to 1/4 in. diam at 1300°F prior to machining of the specimens for hydrogenation and testing. The a-p C-11OM alloy was hydrogenated prior to hot swaging to 1/4 in. roc1 at 1300°F. Hydrogenation prior to fabrication permitted testing of the a-P alloy in the equilibrated and stabilized condition. The equilibration and stabilization treatment used was an air anneal for 1 hr at 1300°F, followed by furnace cooling to 1100°F and then air cooling. Hydrogenation was done in a Sieverts apparatus described previously.' The hydrogenation treatment consisted of heating for 1/4 to 1/2 hr at 820 °C in purified hydrogen, slow cooling to 680"C, holding 1 hr for homogenization, and rapid cooling to room temperature. Intended hydrogen levels for the a-tita-nium materials were 0.05, 0.5, 1.0, 1.5, and 2.0 atomic pct—about 15 to 430 ppm. For the Ti-8 pct Mn alloy, the intended hydrogen levels were 0.05, 0.5, 1.0, 2.5, and 5.0 atomic pct—about 15 to 1100 ppm. The material for the 0.5 atomic pct level of hydrogen was vacuum annealed prior to hydrogenation to increase the accuracy of the addition. Vacuum annealing to remove hydrogen consisted of heating for 6 hr at 820°C, and resulted in a hydrogen content of about 10 to 15 ppm. When hydrogen contents were above 0.5 atomic pct—100 ppm—the hydrogen was added without prior vacuum annealing.

Jan 1, 1957

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Jan 1, 1938

By M. B. Bever, J. E. Reynolds

IN several alloys of iron, copper, and lithium as well as in some pure metals, martensite formed on cooling reverts to the parent phase upon heating to a temperature below the equilibrium temperature at which the parent phase becomes stable.' These martensitic transformations, therefore, are thermally reversible, although appreciable hysteresis may be involved. The martensitic reaction has long been

Jan 1, 1953

By Rafael Errazuriz

About eighty miles north of the city of Antofagasta, Chile, located just below the Tropic of Capricorn, there spreads a wide desert area where copper oxide outcrops can be seen with the naked eye. Numerous old mining works and dump heaps with the green of atacamite and chrisocolla shining in the blazing sun, attest to the work done by miners in the beginning of this century. The dry desert air preserves the footstep marks, paths and trails of old cartwheels from years back. The mining area known as Michilla and Panizos Blancos, is located on the high plateau at 3000 ft above sea level. Around 1920 a Bleichert ropeway was built, which carried ores from the best known mine to a wharf at the Michilla bay. High grade silicious ores were shipped to the Gatico Smelter further north or to smelters in the United States or Japan.

Jan 8, 1973

By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE poor high-temperature oxidation resistance of the refractory metals becomes an important problem as higher operating temperatures are sought. A meaningful analysis of their oxidation behavior requires a knowledge of the phases that can appear during oxidation as well as their relative stability. Although several extensive investigations have been carried out to obtain this information for the W-0 system,1-10 serious inconsistencies still remain. First, the standard free energies of formation (AG°) determined in recent studies which used the solid electrolyte galvanic cell technique6,7,9 differ significantly from those obtained primarily from gas equilibration measurements.1,3,4,10 The disagreement is especially large for the highest oxides. These data have been used to predict the decomposition temperatures of WO2. 72 and WO2.90.1 A considerable extrapolation is required, resulting in a large uncertainty in the decomposition temperatures. Second, Bousquet and perachon3 have presented convincing evidence, ob- tained by gas equilibration measurements, in support of the long-contested existence of W30. Phillips and chang,ll on the other hand, were not able to observe this phase under similar experimental conditions. The purposes of this work, which is part of a continuing investigation of the W-Mo system, were to resolve the discrepancies between the AGO measured by gas equilibration and solid electrolyte galvanic cell techniques, to extend the latter measurements to lower temperatures, to redetermine the WO2.72 and WO2.90 decomposition temperatures, and to apply the more sensitive electromotive-force method to the question of the existence of W3O. I) EXPERIMENTAL PROCEDURE The measurement of ?G° of reaction by the use of calcia-stabilized zirconia solid electrolyte galvanic cells has been described previously.12 The method is based on the measurement of the difference in chemical potential of oxygen between an electrode containing the two oxides of interest and a reference electrode of known oxygen activity. Two different types of cell holders were used in this study. The first type of apparatus has been described earlier." It consisted of two solid electrodes separated by a disc of electrolyte. Both electrodes were exposed to the same stream of purified helium. With this design a gaseous transport of oxygen between the two electrodes is possible. The second type of apparatus, which has also been described earlier,14 effectively separated the two electrode atmospheres. It utilized a closed-end impervious, calcia-stabilized zirconia tube that was open to the atmosphere. The tube served as an electrolyte for the cell and provided a means for separating the anode compartment, which was held under a static vacuum, from an air reference cathode. The cells and reactions of interest are described in Table I. High-purity tungsten metal was obtained from the Fansteel Metallurgical Corp. and the Allied Chemical Corp. Table II contains an analysis of each material. WO3 was prepared by oxidizing the metal in air at approximately 600°C in high-purity recrystallized alumina boats and by the dehydration of reagent-grade tungstic acid in alundum boats. The two methods of preparing WO3 resulted in slightly different purities.

Jan 1, 1968